CN110947403A - Ag3PO4-BiVO4Heterojunction-supported porous carbon photocatalytic degradation material and preparation method thereof - Google Patents
Ag3PO4-BiVO4Heterojunction-supported porous carbon photocatalytic degradation material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 29
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 37
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 229910000397 disodium phosphate Inorganic materials 0.000 claims abstract description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 230000015556 catabolic process Effects 0.000 claims abstract 4
- 238000006731 degradation reaction Methods 0.000 claims abstract 4
- 239000002904 solvent Substances 0.000 claims description 78
- 229920001661 Chitosan Polymers 0.000 claims description 69
- 238000010438 heat treatment Methods 0.000 claims description 69
- 238000003756 stirring Methods 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 45
- 239000012265 solid product Substances 0.000 claims description 32
- 239000012153 distilled water Substances 0.000 claims description 29
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 23
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 18
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 101710134784 Agnoprotein Proteins 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- UUYKGYZJARXSGB-UHFFFAOYSA-N ethanol;ethoxy(trihydroxy)silane Chemical compound CCO.CCO[Si](O)(O)O UUYKGYZJARXSGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000007146 photocatalysis Methods 0.000 claims 3
- 239000003125 aqueous solvent Substances 0.000 claims 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 8
- 229910000161 silver phosphate Inorganic materials 0.000 abstract description 7
- 150000003384 small molecules Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000006479 redox reaction Methods 0.000 abstract description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 3
- 229940012189 methyl orange Drugs 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
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- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000006698 induction Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 90
- 238000001816 cooling Methods 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 7
- 239000005457 ice water Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
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- 231100000719 pollutant Toxicity 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 3
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- 239000010865 sewage Substances 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
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- 239000010842 industrial wastewater Substances 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
The invention relates to the technical field of photocatalytic adsorption materials, and discloses Ag3PO4‑BiVO4Heterojunction loaded porous carbon photocatalytic degradation material and preparation method thereof, and packageThe formula comprises the following raw materials: AgNO3、Na2HPO4Nano BiVO4And silicon-doped porous carbon material. The Ag is3PO4‑BiVO4Heterojunction loaded porous carbon photocatalytic degradation material and preparation method thereof, and Ag formed by using material3PO4‑BiVO4A heterojunction structure, reduces BiVO4The recombination rate of photo-generated electrons and holes, the holes can react with water molecules to generate hydroxyl radicals, and the hydroxyl radicals react with organic pollutants such as phenol, methyl orange and the like to perform oxidation-reduction reaction, and Ag3PO4Formation of delocalized pi in the conduction band*Bond, PO at the same time4 3‑Has induction effect, promotes the separation of photo-generated electrons and holes, and the silicon-doped porous carbon material has rich pore structure and large specific surface area, so that Ag is ensured3PO4‑BiVO4The heterojunction is uniformly dispersed and loaded, and BiVO is avoided4Agglomeration and caking in water, porous carbon material to Cu2+、Hg+、Cd2+Heavy metal ions, and small molecules generated by the degradation of organic pollutants.
Description
Technical Field
The invention relates to the field of photocatalytic adsorption materials, in particular to Ag3PO4-BiVO4A heterojunction loaded porous carbon photocatalytic degradation material and a preparation method thereof.
Background
In recent years, due to the continuous development of the industrialization process, the environmental pollution problem is more and more severe, wherein the water pollution problem is the most prominent, the water pollution problem is mainly caused by that untreated industrial wastewater, untreated domestic sewage, agricultural sewage and the like are directly discharged into the natural water body environment without being treated, and the pollutants mainly comprise inorganic pollutants such as copper, cadmium, mercury heavy metal compounds and ions thereof; halide, phenol, organic dye and other organic pollutants.
The traditional sewage treatment mode adopts the principle of purification, and utilizes physical and chemical methods to convert and absorb harmful substances, such as physical adsorption method, flocculation method and compression precipitation method, etc., and the chemical methods mainly include neutralization method, chemical precipitation method and oxidation-reduction method, etc., and the photodegradation method is a novel water pollution treatment method for decomposing homologies with less carbon atoms by using light energy to promote photocatalyst, and the photocatalyst can produce free radicals with strong activity under the action of light, and can produce addition, substitution and oxidation-reduction reactions with organic pollutants to degrade the pollutants into small molecules with less pollution, and the current photocatalytic material mainly contains TiO2Semiconductor composite material, ZnO composite material, and g-C3N4Heterojunction composite material, etc., BiVO4Has good light response performance, is a photocatalytic material with great potential, but the current BiVO4The photoproduction electrons-holes generated by the semiconductor material are easy to recombine, and the BiVO is greatly reduced4Photocatalytic activity of semiconductor material, and BiVO4Has good dispersibility in waterThe photocatalyst material has the advantages of being poor in performance, easy to agglomerate and agglomerate among molecules, preventing the photocatalytic material from rapidly responding to and absorbing light energy, reducing the contact area with pollutants and reducing the photocatalytic activity of the photocatalytic material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides Ag3PO4-BiVO4The heterojunction loaded porous carbon photocatalytic degradation material and the preparation method thereof solve the problem of BiVO4The problem that photo-generated electrons and holes generated by the semiconductor material are easy to recombine is solved, and the BiVO is also solved4Poor dispersibility in water, easy agglomeration and caking among molecules.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: ag3PO4-BiVO4The heterojunction loaded porous carbon photocatalytic degradation material comprises the following formula raw materials in parts by weight: 18-25 parts of AgNO35-7 parts of Na2HPO416-22 parts of nano BiVO4And 46-61 parts of silicon-doped porous carbon material.
Preferably, the preparation method of the silicon-doped porous carbon material comprises the following steps:
(1) adding an ethanol solvent into a reaction bottle, adding glacial acetic acid to adjust the pH value of the solution to 2-3, adding chitosan, stirring until the chitosan is dissolved, adding trimesic acid and a catalyst p-toluenesulfonic acid, placing the reaction bottle in an oil bath, heating to 80-90 ℃, stirring at a constant speed for reaction for 30-35 h, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing a solid product by using a proper amount of distilled water and an ether solvent, and fully drying to prepare the trimestriylated chitosan.
(2) Adding a distilled water solvent and the triphenyl esterified chitosan into a reaction bottle, stirring at a constant speed, dropwise adding a hydrochloric acid solution until the solid is dissolved, slowly dropwise adding an ethanol solution of ethyl orthosilicate, placing the reaction bottle in a constant-temperature water bath kettle, heating to 40-50 ℃, stirring at a constant speed for 5-8 hours until a sol is formed, placing the reaction bottle in a forced air drying oven, heating to 80-90 ℃, and drying the solvent to prepare the silicon-based esterified chitosan composite material.
(3) Placing the silicon-based-esterified chitosan composite material in an atmosphere resistance furnace, wherein the heating rate is 5-10 ℃/min, and the temperature is 920-950 ℃ under2Calcining for 2-3h in the atmosphere to obtain the calcined product, namely the silicon-doped porous carbon material.
Preferably, the mass ratio of the chitosan to the trimesic acid to the p-toluenesulfonic acid is 12-15:18-24: 1.
Preferably, the mass ratio of the s-triphenyl esterified chitosan to the tetraethoxysilane is 20-28: 1.
Preferably, the nano BiVO4The preparation method comprises the following steps:
(1) adding ethanol solvent and Bi (NO) into a reaction bottle3)3And VCl3Placing the reaction bottle in an ultrasonic dispersion instrument, heating to 40-50 ℃, carrying out ultrasonic dispersion treatment for 1-2h, heating the solution to 120-130 ℃, carrying out uniform stirring reflux reaction for 25-30h, cooling the solution to room temperature, carrying out reduced pressure concentration to remove the solvent, and fully drying the solid product.
(2) Placing the solid product in a resistance furnace, heating at a rate of 3-5 ℃/min, calcining at 460-480 ℃ for 2-3h, washing the calcined product with a proper amount of ethanol solvent, and fully drying to obtain the nano BiVO4。
Preferably, said Bi (NO)3)3And VCl3The molar ratio of the substances is 1-1.1: 1.
Preferably, the Ag is3PO4-BiVO4The preparation method of the heterojunction loaded porous carbon photocatalytic degradation material comprises the following steps:
(1) adding distilled water solvent and 18-25 parts of AgNO into a reaction bottle35-7 parts of Na2HPO4And 16-22 parts of nano BiVO4Placing a reaction bottle in an ultrasonic disperser, heating to 50-60 ℃, carrying out ultrasonic dispersion treatment for 2-3h at the ultrasonic frequency of 22-25 KHz, placing the reaction bottle in a constant-temperature water bath, heating to 70-80 ℃, carrying out uniform stirring reaction for 1-2h, adding 46-61 parts of silicon-doped porous carbon material, carrying out uniform stirring for 4-6 h,cooling the solution in ice water bath, filtering the solution to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to obtain the Ag3PO4-BiVO4The heterojunction supports porous carbon photocatalytic degradation material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the Ag is3PO4-BiVO4A heterojunction loaded porous carbon photocatalytic degradation material and a preparation method thereof, which uses Ag3PO4In-situ growth on nano BiVO4Forming Ag on the surface of3PO4-BiVO4A heterojunction structure, greatly reduced BiVO4The recombination rate of photo-generated electrons and holes increases the number of strong oxidative holes, the holes can react with water molecules to generate hydroxyl radicals, and the hydroxyl radicals and the organic pollutants such as phenol, methyl orange and the like react with redox reaction under the action of the holes and the hydroxyl radicals to degrade the pollutants into small molecules, and Ag3PO4And BiVO4Schottky barrier is formed between the semiconductors, and BiVO is increased through rectification4The conduction band potential of the BiVO is accelerated4The separation of photo-generated electrons and holes improves the photocatalytic activity of the material, and Ag3PO4The band gap is narrow, the light absorption waveband is wide, the utilization rate of the photocatalytic material to light energy is increased, and delocalization pi is formed in a conduction band*Bond, PO at the same time4 3-Has inducing effect, and promotes the separation of photo-generated electrons and holes under the synergistic effect.
The Ag is3PO4-BiVO4The heterojunction loaded porous carbon photocatalytic degradation material and the preparation method thereof, the triphenyl esterified chitosan has a three-dimensional branched structure, porous carbon with rich pores is formed by calcination, and silicon is doped on the surface of the porous carbon to form micro-cracks and mesoporous structures, so that the specific surface area of the porous carbon is increased, and Ag can be made3PO4-BiVO4The heterojunction is uniformly dispersed and loaded on the surface of the porous carbon, thereby avoiding BiVO4The dispersion in water is poor, so that agglomeration and caking are caused, and the photoresponse and the light energy absorption rate of the photocatalytic material are increased.
The Ag is3PO4-BiVO4The heterojunction loaded porous carbon photocatalytic degradation material and the preparation method thereof, the silicon-doped porous carbon material has rich pore structure and can be used as an adsorbent for Cu2+、Hg+、Cd2+The heavy metal ions are physically adsorbed and can be effectively adsorbed with small molecules generated by degrading organic pollutants by the photocatalyst, so that secondary pollution of degradation products is avoided.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: ag3PO4-BiVO4The heterojunction loaded porous carbon photocatalytic degradation material comprises the following formula raw materials in parts by weight: 18-25 parts of AgNO35-7 parts of Na2HPO416-22 parts of nano BiVO4And 46-61 parts of silicon-doped porous carbon material.
The preparation method of the silicon-doped porous carbon material comprises the following steps:
(1) adding an ethanol solvent into a reaction bottle, adding glacial acetic acid to adjust the pH value of the solution to 2-3, adding chitosan, stirring until the chitosan is dissolved, adding trimesic acid and a catalyst p-toluenesulfonic acid in a mass ratio of 12-15:18-24:1, placing the reaction bottle in an oil bath pot, heating to 80-90 ℃, uniformly stirring for reaction for 30-35 hours, cooling the solution to room temperature, carrying out reduced pressure concentration to remove the solvent, washing the solid product by using a proper amount of distilled water and an ether solvent, and fully drying to obtain the trimestriylated chitosan.
(2) Adding a distilled water solvent and the triphenyl esterified chitosan into a reaction bottle, stirring at a constant speed, dropwise adding a hydrochloric acid solution until a solid is dissolved, slowly dropwise adding an ethyl orthosilicate ethanol solution, wherein the mass ratio of the triphenyl esterified chitosan to the ethyl orthosilicate is 20-28:1, heating the reaction bottle in a constant-temperature water bath kettle to 40-50 ℃, stirring at a constant speed for 5-8 hours until a sol is formed, placing the reaction bottle in a blast drying box, heating to 80-90 ℃, and drying the solvent to prepare the silicon-based-esterified chitosan composite material.
(3) Placing the silicon-based-esterified chitosan composite material in an atmosphere resistance furnace, wherein the heating rate is 5-10 ℃/min, and the temperature is 920-950 ℃ under2Calcining for 2-3h in the atmosphere to obtain the calcined product, namely the silicon-doped porous carbon material.
Nano BiVO4The preparation method comprises the following steps:
(1) adding ethanol solvent and Bi (NO) into a reaction bottle3)3And VCl3And the mass molar ratio of the two substances is 1-1.1:1, placing the reaction bottle in an ultrasonic dispersion instrument, heating to 40-50 ℃, carrying out ultrasonic dispersion treatment for 1-2h, heating the solution to 120-130 ℃, carrying out uniform stirring reflux reaction for 25-30h, cooling the solution to room temperature, carrying out reduced pressure concentration to remove the solvent, and fully drying the solid product.
(2) Placing the solid product in a resistance furnace, heating at a rate of 3-5 ℃/min, calcining at 460-480 ℃ for 2-3h, washing the calcined product with a proper amount of ethanol solvent, and fully drying to obtain the nano BiVO4。
Ag3PO4-BiVO4The preparation method of the heterojunction loaded porous carbon photocatalytic degradation material comprises the following steps:
(1) adding distilled water solvent and 18-25 parts of AgNO into a reaction bottle35-7 parts of Na2HPO4And 16-22 parts of nano BiVO4Placing a reaction bottle in an ultrasonic disperser, heating to 50-60 ℃, carrying out ultrasonic dispersion treatment for 2-3h at the ultrasonic frequency of 22-25 KHz, placing the reaction bottle in a constant-temperature water bath, heating to 70-80 ℃, uniformly stirring for reaction for 1-2h, adding 46-61 parts of silicon-doped porous carbon material, uniformly stirring for 4-6 h, placing the solution in an ice-water bath for cooling, filtering the solution to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the Ag-doped porous carbon material3PO4-BiVO4The heterojunction supports porous carbon photocatalytic degradation material.
Example 1
(1) Preparing a homotriphenized chitosan component 1: adding an ethanol solvent into a reaction bottle, adding glacial acetic acid to adjust the pH value of the solution to 3, adding chitosan, stirring until the chitosan is dissolved, adding trimesic acid and a catalyst p-toluenesulphonic acid in a mass ratio of 12:18:1, placing the reaction bottle into an oil bath pot, heating to 80 ℃, stirring at a constant speed for reaction for 30 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing a solid product by using a proper amount of distilled water and an ether solvent, and fully drying to obtain a trimestriylated chitosan component 1.
(2) Preparation of silicon-based-esterified chitosan composite material 1: adding a distilled water solvent and the triphenyl esterified chitosan component 1 into a reaction bottle, stirring at a constant speed, dropwise adding a hydrochloric acid solution until a solid is dissolved, slowly dropwise adding an ethyl orthosilicate ethanol solution, wherein the mass ratio of the triphenyl esterified chitosan component 1 to the ethyl orthosilicate is 20:1, placing the reaction bottle into a constant-temperature water bath kettle, heating to 40 ℃, stirring at a constant speed for 5 hours until a sol state is formed, placing the reaction bottle into a blast drying box, heating to 80 ℃, and drying the solvent to obtain the silicon-based esterified chitosan composite material 1.
(3) Preparing a silicon-doped porous carbon material 1: placing the silicon-based-esterified chitosan composite material 1 in an atmosphere resistance furnace, wherein the heating rate is 5 ℃/min, and N is carried out at 920 DEG C2Calcining for 2h in the atmosphere to obtain the calcined product, namely the silicon-doped porous carbon material 1.
(4) Preparation of nano BiVO4Compound 1: adding ethanol solvent and Bi (NO) into a reaction bottle3)3And VCl3Placing a reaction bottle in an ultrasonic disperser, heating to 40 ℃, performing ultrasonic dispersion treatment for 1 h, heating the solution to 120 ℃, stirring at a constant speed and refluxing for reaction for 25 h, cooling the solution to room temperature, performing reduced pressure concentration to remove the solvent, fully drying the solid product, placing the solid product in a resistance furnace, heating at the rate of 3 ℃/min, performing heat preservation and calcination at 460 ℃ for 2h, washing the calcined product with a proper amount of ethanol solvent, and fully drying to prepare the nano BiVO4Compound 1.
(5) Preparation of Ag3PO4-BiVO4Heterojunction-supported porous carbon photocatalytic degradation material 1: towards the reactionAdding distilled water solvent and 18 parts of AgNO into a bottle35 parts of Na2HPO4And 16 parts of nano BiVO4Placing a reaction bottle in an ultrasonic disperser, heating to 50 ℃, carrying out ultrasonic dispersion treatment for 2h at the ultrasonic frequency of 22 KHz, placing the reaction bottle in a constant-temperature water bath kettle, heating to 70 ℃, carrying out uniform stirring reaction for 1 h, then adding 61 parts of silicon-doped porous carbon material 1, carrying out uniform stirring for 4 h, placing the solution in an ice-water bath for cooling, filtering the solution to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the Ag3PO4-BiVO4The heterojunction supports porous carbon photocatalytic degradation material 1.
Example 2
(1) Preparing a triphenyl esterified chitosan component 2: adding an ethanol solvent into a reaction bottle, adding glacial acetic acid to adjust the pH value of the solution to 2, adding chitosan, stirring until the chitosan is dissolved, adding trimesic acid and a catalyst p-toluenesulphonic acid in a mass ratio of 12:20:1, placing the reaction bottle in an oil bath pot, heating to 90 ℃, stirring at a constant speed for reaction for 35 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing a solid product by using a proper amount of distilled water and an ether solvent, and fully drying to obtain a trimestriylated chitosan component 2.
(2) Preparation of silicon-based-esterified chitosan composite 2: adding a distilled water solvent and a triphenyl esterified chitosan component 2 into a reaction bottle, stirring at a constant speed, dropwise adding a hydrochloric acid solution until a solid is dissolved, slowly dropwise adding an ethyl orthosilicate ethanol solution, wherein the mass ratio of the triphenyl esterified chitosan component 2 to the ethyl orthosilicate is 28:1, placing the reaction bottle in a constant-temperature water bath kettle, heating to 40 ℃, stirring at a constant speed for 8 hours until a sol is formed, placing the reaction bottle in a blast drying box, heating to 80 ℃, and drying the solvent to obtain the silicon-based esterified chitosan composite material 2.
(3) Preparation of silicon-doped porous carbon material 2: placing the silicon-based-esterified chitosan composite material 2 in an atmosphere resistance furnace, wherein the heating rate is 5 ℃/min, and the temperature is 950 ℃, and N is2Calcining for 2h in the atmosphere to obtain a calcined product, namely the silicon-doped porous carbon material 2.
(4) Preparation of nano BiVO4Compound 2: adding ethanol solvent and Bi (NO) into a reaction bottle3)3And VCl3Placing a reaction bottle in an ultrasonic disperser, heating to 40 ℃, performing ultrasonic dispersion treatment for 1 h, heating the solution to 130 ℃, stirring at a constant speed and refluxing for reaction for 25 h, cooling the solution to room temperature, performing reduced pressure concentration to remove the solvent, fully drying the solid product, placing the solid product in a resistance furnace, heating at the rate of 3 ℃/min, performing heat preservation and calcination at 460 ℃ for 3h, washing the calcined product with a proper amount of ethanol solvent, and fully drying to prepare the nano BiVO4Compound 2.
(5) Preparation of Ag3PO4-BiVO4Heterojunction loading porous carbon photocatalytic degradation material 2: adding distilled water solvent and 19.5 parts of AgNO into a reaction bottle35.5 parts of Na2HPO4And 17.5 parts of nano BiVO4Placing a reaction bottle in an ultrasonic disperser, heating to 50 ℃, carrying out ultrasonic dispersion treatment for 2h at the ultrasonic frequency of 22 KHz, placing the reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, carrying out uniform stirring reaction for 2h, adding 57.5 parts of silicon-doped porous carbon material 2, carrying out uniform stirring for 4 h, placing the solution in an ice-water bath for cooling, filtering the solution to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the Ag-doped porous carbon material3PO4-BiVO4The heterojunction supports porous carbon photocatalytic degradation material 2.
Example 3
(1) Preparing a triphenyl esterified chitosan component 3: adding ethanol solvent into a reaction bottle, adding glacial acetic acid to adjust the pH value of the solution to 2, adding chitosan, stirring until the chitosan is dissolved, adding trimesic acid and catalyst p-toluenesulphonic acid, wherein the mass ratio of the trimesic acid to the catalyst p-toluenesulphonic acid is 15:24:1, placing the reaction bottle into an oil bath pot, heating to 80 ℃, stirring at a constant speed for reaction for 35 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing a solid product by using a proper amount of distilled water and ether solvent, and fully drying to obtain a trimestriylated chitosan component 3.
(2) Preparation of silicon-based-esterified chitosan composite material 3: adding a distilled water solvent and a triphenyl esterified chitosan component 3 into a reaction bottle, stirring at a constant speed, dropwise adding a hydrochloric acid solution until a solid is dissolved, slowly dropwise adding an ethyl orthosilicate ethanol solution, wherein the mass ratio of the triphenyl esterified chitosan component 3 to the ethyl orthosilicate is 20:1, placing the reaction bottle into a constant-temperature water bath kettle, heating to 50 ℃, stirring at a constant speed for 5 hours until a sol is formed, placing the reaction bottle into a blast drying box, heating to 90 ℃, and drying the solvent to obtain the silicon-based esterified chitosan composite material 3.
(3) Preparation of silicon-doped porous carbon material 3: placing the silicon-based-esterified chitosan composite material 3 in an atmosphere resistance furnace, wherein the heating rate is 10 ℃/min, and the temperature is 920 ℃ under N2Calcining for 3h in the atmosphere to obtain a calcined product, namely the silicon-doped porous carbon material 3.
(4) Preparation of nano BiVO4Compound 3: adding ethanol solvent and Bi (NO) into a reaction bottle3)3And VCl3Placing a reaction bottle in an ultrasonic disperser, heating to 40 ℃, performing ultrasonic dispersion treatment for 1 h, heating the solution to 120 ℃, stirring at a constant speed and refluxing for reaction for 25 h, cooling the solution to room temperature, performing reduced pressure concentration to remove the solvent, fully drying the solid product, placing the solid product in a resistance furnace, heating at a rate of 5 ℃/min, performing heat preservation and calcination at 460 ℃ for 2h, washing the calcined product with a proper amount of ethanol solvent, and fully drying to prepare the nano BiVO4Compound 3.
(5) Preparation of Ag3PO4-BiVO4Heterojunction loading porous carbon photocatalytic degradation material 3: adding distilled water solvent and 21.5 parts of AgNO into a reaction bottle36 parts of Na2HPO4And 19 parts of nano BiVO4Placing a reaction bottle in an ultrasonic disperser, heating to 60 ℃, carrying out ultrasonic dispersion treatment for 2h at the ultrasonic frequency of 22 KHz, placing the reaction bottle in a constant-temperature water bath, heating to 80 ℃, carrying out uniform stirring reaction for 2h, then adding 53.5 parts of silicon-doped porous carbon material 3, carrying out uniform stirring for 4 h, placing the solution in an ice-water bath for cooling, filtering the solution to remove the solvent, washing the solid product with a proper amount of distilled water, and fully dryingTo prepare Ag3PO4-BiVO4The heterojunction supports porous carbon photocatalytic degradation material 3.
Example 4
(1) Preparing a triphenyl esterified chitosan component 4: adding an ethanol solvent into a reaction bottle, adding glacial acetic acid to adjust the pH value of the solution to 2, adding chitosan, stirring until the chitosan is dissolved, adding trimesic acid and a catalyst p-toluenesulphonic acid in a mass ratio of 14:22:1, placing the reaction bottle in an oil bath pot, heating to 85 ℃, stirring at a constant speed for reaction for 32 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing a solid product by using a proper amount of distilled water and an ether solvent, and fully drying to obtain a trimestriylated chitosan component 4.
(2) Preparation of the silicon-based-esterified chitosan composite 4: adding a distilled water solvent and a triphenyl esterified chitosan component 4 into a reaction bottle, stirring at a constant speed, dropwise adding a hydrochloric acid solution until a solid is dissolved, slowly dropwise adding an ethyl orthosilicate ethanol solution, wherein the mass ratio of the triphenyl esterified chitosan component 4 to the ethyl orthosilicate is 24:1, placing the reaction bottle in a constant-temperature water bath kettle, heating to 45 ℃, stirring at a constant speed for 6 hours until a sol is formed, placing the reaction bottle in a blast drying box, heating to 85 ℃, and drying the solvent to obtain the silicon-based esterified chitosan composite material 4.
(3) Preparation of silicon-doped porous carbon material 4: placing the silicon-based-esterified chitosan composite material 4 in an atmosphere resistance furnace, wherein the heating rate is 10 ℃/min, and the temperature is 930 ℃ and N2Calcining for 2.5 h in the atmosphere to obtain a calcined product, namely the silicon-doped porous carbon material 4.
(4) Preparation of nano BiVO4Compound 4: adding ethanol solvent and Bi (NO) into a reaction bottle3)3And VCl3Placing a reaction bottle in an ultrasonic disperser, heating to 45 ℃, performing ultrasonic dispersion treatment for 1.5h, heating the solution to 125 ℃, stirring at a constant speed and refluxing for reaction for 28 h, cooling the solution to room temperature, performing reduced pressure concentration to remove the solvent, fully drying the solid product, placing the solid product in a resistance furnace, heating at a rate of 4 ℃/min, and performing heat preservation and calcination at 470 ℃ for 2.5 h to ensure that the mass molar ratio of the two substances is 1.05:1Washing the calcined product with a proper amount of ethanol solvent, and fully drying to prepare the nano BiVO4Compound 4.
(5) Preparation of Ag3PO4-BiVO4Heterojunction loading porous carbon photocatalytic degradation material 4: adding distilled water solvent and 23 parts of AgNO into a reaction bottle36.5 parts of Na2HPO4And 20.5 parts of nano BiVO4And (2) placing a reaction bottle into an ultrasonic disperser, heating to 60 ℃, carrying out ultrasonic dispersion treatment for 2.5 hours at the ultrasonic frequency of 25 KHz, placing the reaction bottle into a constant-temperature water bath kettle, heating to 75 ℃, carrying out uniform stirring reaction for 1.5 hours, adding 50 parts of silicon-doped porous carbon material 4, carrying out uniform stirring for 5 hours, placing the solution into an ice-water bath for cooling, filtering the solution to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the Ag-doped porous carbon material3PO4-BiVO4The heterojunction supports a porous carbon photocatalytic degradation material 4.
Example 5
(1) Preparing a 5-triphenyl esterified chitosan component: adding ethanol solvent into a reaction bottle, adding glacial acetic acid to adjust the pH value of the solution to 2, adding chitosan, stirring until the chitosan is dissolved, adding trimesic acid and catalyst p-toluenesulphonic acid, wherein the mass ratio of the trimesic acid to the catalyst p-toluenesulphonic acid is 15:24:1, placing the reaction bottle into an oil bath pot, heating to 90 ℃, stirring at a constant speed for reaction for 35 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing a solid product by using a proper amount of distilled water and ether solvent, and fully drying to obtain a trimestriylated chitosan component 5.
(2) Preparation of the silicon-based-esterified chitosan composite 5: adding a distilled water solvent and a triphenyl esterified chitosan component 5 into a reaction bottle, stirring at a constant speed, dropwise adding a hydrochloric acid solution until a solid is dissolved, slowly dropwise adding an ethyl orthosilicate ethanol solution, wherein the mass ratio of the triphenyl esterified chitosan component 5 to the ethyl orthosilicate is 28:1, placing the reaction bottle into a constant-temperature water bath kettle, heating to 50 ℃, stirring at a constant speed for 8 hours until a sol is formed, placing the reaction bottle into a blast drying box, heating to 90 ℃, and drying the solvent to obtain the silicon-based esterified chitosan composite material 5.
(3) Preparation of silicon-doped porous carbon material 5: placing the silicon-based-esterified chitosan composite material 5 in an atmosphere resistance furnace, wherein the heating rate is 10 ℃/min, and the temperature is 950 ℃, and N is2Calcining for 3h in the atmosphere to obtain a calcined product, namely the silicon-doped porous carbon material 5.
(4) Preparation of nano BiVO4Compound 5: adding ethanol solvent and Bi (NO) into a reaction bottle3)3And VCl3Placing a reaction bottle in an ultrasonic disperser, heating to 50 ℃, performing ultrasonic dispersion treatment for 2 hours, heating the solution to 130 ℃, stirring at a constant speed and refluxing for reaction for 30 hours, cooling the solution to room temperature, performing reduced pressure concentration to remove the solvent, fully drying the solid product, placing the solid product in a resistance furnace, heating at a rate of 5 ℃/min, performing heat preservation and calcination at 480 ℃ for 3 hours, washing the calcined product with a proper amount of ethanol solvent, and fully drying to prepare the nano BiVO4Compound 5.
(5) Preparation of Ag3PO4-BiVO4Heterojunction supported porous carbon photocatalytic degradation material 5: adding distilled water solvent and 25 parts of AgNO into a reaction bottle37 parts of Na2HPO4And 22 parts of nano BiVO4Placing a reaction bottle in an ultrasonic disperser, heating to 60 ℃, carrying out ultrasonic dispersion treatment for 3 hours at the ultrasonic frequency of 25 KHz, placing the reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, carrying out uniform stirring reaction for 2 hours, then adding 46 parts of silicon-doped porous carbon material 5, carrying out uniform stirring for 6 hours, placing the solution in an ice-water bath for cooling, filtering the solution to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the Ag3PO4-BiVO4The heterojunction supports a porous carbon photocatalytic degradation material 5.
In summary, the Ag3PO4-BiVO4A heterojunction loaded porous carbon photocatalytic degradation material and a preparation method thereof, which uses Ag3PO4In-situ growth on nano BiVO4Forming Ag on the surface of3PO4-BiVO4A heterojunction structure, greatly reduced BiVO4The recombination rate of the photo-generated electrons and holes,the number of strong oxidizing cavities is increased, the cavities can react with water molecules to generate hydroxyl radicals, and the hydroxyl radicals and organic pollutants such as phenol, methyl orange and the like react with the cavities to perform redox reaction under the action of the hydroxyl radicals, so that the pollutants are degraded into small molecules, and Ag3PO4And BiVO4Schottky barrier is formed between the semiconductors, and BiVO is increased through rectification4The conduction band potential of the BiVO is accelerated4The separation of photo-generated electrons and holes improves the photocatalytic activity of the material, and Ag3PO4The band gap is narrow, the light absorption waveband is wide, the utilization rate of the photocatalytic material to light energy is increased, and delocalization pi is formed in a conduction band*Bond, PO at the same time4 3-Has inducing effect, and promotes the separation of photo-generated electrons and holes under the synergistic effect.
The triphenyl esterified chitosan has a three-dimensional branched structure, porous carbon with rich pores is formed by calcination, and silicon is doped on the surface of the porous carbon to form micro-cracks and mesoporous structures, so that the specific surface area of the porous carbon is increased, and Ag can be made3PO4-BiVO4The heterojunction is uniformly dispersed and loaded on the surface of the porous carbon, thereby avoiding BiVO4The dispersion in water is poor, so that agglomeration and caking are caused, and the photoresponse and the light energy absorption rate of the photocatalytic material are increased.
The silicon-doped porous carbon material has rich pore structure and can be used as an adsorbent for Cu2+、Hg+、Cd2+The heavy metal ions are physically adsorbed and can be effectively adsorbed with small molecules generated by degrading organic pollutants by the photocatalyst, so that secondary pollution of degradation products is avoided.
Claims (7)
1. Ag3PO4-BiVO4The heterojunction-supported porous carbon photocatalytic degradation material comprises the following formula raw materials in parts by weight, and is characterized in that: 18-25 parts of AgNO35-7 parts of Na2HPO416-22 parts of nano BiVO4And 46-61 parts of silicon-doped porous carbon material.
2. Ag according to claim 13PO4-BiVO4The heterojunction load porous carbon photocatalysis degradation material is characterized in that: the preparation method of the silicon-doped porous carbon material comprises the following steps:
(1) adding glacial acetic acid into an ethanol solvent to adjust the pH value of the solution to 2-3, adding chitosan, trimesic acid and a catalyst p-toluenesulfonic acid, heating the solution to 80-90 ℃, reacting for 30-35 h, removing the solvent from the solution, washing a solid product, and drying to prepare trimesic esterified chitosan;
(2) adding triphenyl esterified chitosan into a distilled aqueous solvent, dropwise adding a hydrochloric acid solution until a solid is dissolved, dropwise adding an ethyl orthosilicate ethanol solution, heating the solution to 40-50 ℃, uniformly stirring for 5-8 hours to form a sol, and drying the solution to remove the solvent to prepare the silicon-based esterified chitosan composite material;
(3) placing the silicon-based-esterified chitosan composite material in an atmosphere resistance furnace, wherein the heating rate is 5-10 ℃/min, and the temperature is 920-950 ℃ under2Calcining for 2-3h in the atmosphere to obtain the calcined product, namely the silicon-doped porous carbon material.
3. The silicon-doped porous carbon material of claim 2, wherein: the mass ratio of the chitosan, the trimesic acid and the p-toluenesulfonic acid in the step (1) is 12-15:18-24: 1.
4. The silicon-doped porous carbon material of claim 2, wherein: the mass ratio of the triphenyl esterified chitosan to the ethyl orthosilicate in the step (2) is 20-28: 1.
5. Ag according to claim 13PO4-BiVO4The heterojunction load porous carbon photocatalysis degradation material is characterized in that: the nanometer BiVO4The preparation method comprises the following steps:
(1) adding Bi (NO) to an ethanol solvent3)3And VCl3Carrying out ultrasonic dispersion treatment on the solution at 40-50 ℃ for 1-2h, heating the solution to 120-130 ℃, reacting for 25-30h, removing the solvent from the solution, and drying a solid product;
(2) placing the solid product in a resistance furnace, heating at a rate of 3-5 ℃/min, calcining at 460-480 ℃ for 2-3h, washing the calcined product with a proper amount of ethanol solvent, and fully drying to obtain the nano BiVO4。
6. Nano BiVO according to claim 54The method is characterized in that: the Bi (NO)3)3And VCl3The molar ratio of the substances is 1-1.1: 1.
7. Ag according to claim 13PO4-BiVO4The heterojunction load porous carbon photocatalysis degradation material is characterized in that: the Ag is3PO4-BiVO4The preparation method of the heterojunction loaded porous carbon photocatalytic degradation material comprises the following steps:
(1) adding 18-25 parts of AgNO into distilled water solvent35-7 parts of Na2HPO4And 16-22 parts of nano BiVO4Performing ultrasonic dispersion treatment on the solution at 50-60 ℃ for 2-3h, heating the solution to 70-80 ℃, reacting for 1-2h, adding 46-61 parts of silicon-doped porous carbon material, stirring at constant speed for 4-6 h, removing the solvent from the solution, washing a solid product, and fully drying to prepare the Ag3PO4-BiVO4The heterojunction supports porous carbon photocatalytic degradation material.
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| CN112090445A (en) * | 2020-08-20 | 2020-12-18 | 德华兔宝宝装饰新材股份有限公司 | g-C3N4/TiO2Preparation method and application of nano-composite surface coating chitosan formaldehyde remover |
| CN112830633A (en) * | 2021-01-15 | 2021-05-25 | 上海水生环境工程有限公司 | Method for synergistically purifying conventional and novel pollutants in water |
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| CN112090445A (en) * | 2020-08-20 | 2020-12-18 | 德华兔宝宝装饰新材股份有限公司 | g-C3N4/TiO2Preparation method and application of nano-composite surface coating chitosan formaldehyde remover |
| CN112090445B (en) * | 2020-08-20 | 2023-06-13 | 德华兔宝宝装饰新材股份有限公司 | g-C 3 N 4 /TiO 2 Preparation method and application of nanocomposite surface-coated chitosan formaldehyde remover |
| CN112830633A (en) * | 2021-01-15 | 2021-05-25 | 上海水生环境工程有限公司 | Method for synergistically purifying conventional and novel pollutants in water |
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